Explosive emulsion

Emulsifiers are disclosed which comprise the reaction product of component (I) with component (II). Component (I) comprises the reaction product of certain carboxylic acids or anhydrides, or ester or amide derivatives thereof, with ammonia, at least one amine, at least one alkali and/or at least one alkaline-earth metal. Component (II) comprises certain phosphorous-containing acids; or metal salts of said phosphorous-containing acids, the metals being selected from the group consisting of magnesium, calcium, strontium, chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver zinc, cadmium, aluminum, tin, lead, and mixtures of two or more thereof. These emulsifiers are useful in water-in-oil explosive emulsions.

 

We claim:

1. An explosive emulsion comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, and an emulsifying amount of a composition comprising the reaction product of component (I) with component (II);

component (I) comprising:

(A) the reaction product of

(A)(i) at least one carboxylic acid or anhydride, or ester or amide derived from said acid or anhydride, with

(A)(ii) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal; or

(B) a composition comprising

(B)(i) the reaction product of (B)(i)(a) at least one high-molecular weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derived form said high-molecular weight acid or anhydride, with (B)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(B)(ii) the reaction product of (B)(ii)(a) at least one low-molecular weight carboxylic acid or anhydride, or ester or amide derived from said low-molecular weight acid or anhydride, with (B)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms; or

(C) a composition comprising

(C)(i) the reaction product of (C)(i)(a) at least one high-molecular weight hydrocarbyl-substituted polycarboxylic acid or anhydride, or ester or amide derived from said high-molecular weight polycarboxylic acid or anhydride, with (C)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (C)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(C)(ii) the reaction product of (C)(ii) (a) at least one low-molecular weight polycarboxylic acid or anhydride, or ester or amide derived from said low-molecular weight polycarboxylic acid or anhydride, with (C)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (C)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms;

said components (C)(i) and (C)(ii) being couples together by (C)(iii) at least one compound having (C)(iii)(a) two or more primary amino groups, (C)(iii)(b) two or more secondary amino groups, (C)(iii)(c) at least one primary amino group and at least one secondary amino group, (C)(iii)(d) at least two hydroxyl groups, or (C)(iii)(e) at least one primary or secondary amino group and at least one hydroxyl group; or

(D) mixture of two or more of (A), (B) and (C);

component (II) comprising:

(A') at least one phosphorous-containing acid represented by the formula ##STR34## wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are independently oxygen or sulfur; a and b are independently zero or one, and R.sup.1 and R.sup.2 are independently hydrocarbyl groups; or

(B') at least one salt derived from said phosphorous-containing acid (A') and at least one metal selected from the group consisting of magnesium, calcium, strontium, chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc, cadmium, aluminum, tin, lead, and mixtures of two or more thereof; or

(C') mixture of (A') and (B'); with the proviso that when component (II) is (A'), component (I) is (B), (C) or a mixture of (B) and (C).

2. An explosive emulsion made by combining an oxidizer phase comprising at least one oxygen-supplying component with an organic phase comprising at least one carbonaceous fuel and a composition comprising the reaction product of component (1) with component (II);

component (I) comprising:

(A) the reaction product of

(A)(i) at least one carboxylic acid or anhydride, or ester or amide derived from said acid or anhydride, with

(A)(ii) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal; or

(B) a composition comprising

(B)(i) the reaction product of (B)(i)(a) at least one high-molecular weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derived from said high-molecular weight acid or anhydride, with (B)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(B)(ii) the reaction product of (B)(ii)(a) at least one low-molecular weight carboxylic acid or anhydride, or ester or amide derived form said low-molecular weight acid or anhydride, with (B)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms; or

(C) a composition comprising

(C)(i) the reaction product of (C)(i)(a) at least one high-molecular weight hydrocarbyl-substituted polycarboxylic acid or anhydride, or ester or amide derived form said high-molecular weight polycarboxylic acid or anhydride, with (C)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (C)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(C)(ii) the reaction product of (C)(ii)(a) at least one low-molecular weight polycarboxylic acid or anhydride, or ester or amide derived from said low-molecular weight polycarboxylic acid or anhydride, with (C)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (C)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms;

said components (C)(i) and (C)(ii) being coupled together by (C)(iii) at least one compound having (C)(iii)(a) two or more primary amino groups, (C)(iii)(b) two or more secondary amino groups, (C)(iii)(c) at least one primary amino group and at least one secondary amino group, (C)(iii)(d) at least two hydroxyl groups, or (C)(iii)(e) at least one primary or secondary amino group and at least one hydroxyl group; or

(D) mixture of two or mote of (A), (B) and (C);

component (II) comprising:

(A') at least one phosphorous-containing acid represented by the formula ##STR35## wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are independently oxygen or sulfur; a and b are independently zero or one, and R.sup.1 and R.sup.2 are independently hydrocarbyl groups; or

(B') at least one salt derived from said phosphorous-containing acid (A') and at least one metal selected from the group consisting of magnesium, calcium, strontium, chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc, cadmium, aluminum, tin, lead, and mixtures of two or more thereof; or

(C') mixture of (A') and (B');

with the proviso that when component (II) is (A'), component (I) is (B), (C) or a mixture of (B) and (C).

3. A cap-sensitive explosive emulsion comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, said carbonaceous fuel comprising at least one wax, and an emulsifying amount of a composition comprising the reaction product of component (I) with component (II);

component (I) comprising:

(A) the reaction product of

(A)(i) at least one carboxylic acid or anhydride, or ester or amide derived from said acid or anhydride, with

(A)(ii) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal; or

(B) a composition comprising

(B)(i) the reaction product of (B)(i)(a) at least one high-molecular weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derived form said high-molecular weight acid or anhydride, with (B)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(B)(ii) the reaction product of (B)(ii)(a) at least one low-molecular weight carboxylic acid or anhydride, or ester or amide derived from said low-molecular weight acid or anhydride, with (B)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms; or

(C) a composition comprising

(C)(i) the reaction product of (C)(i)(a) at least one high-molecular weight hydrocarbyl-substituted polycarboxylic acid or anhydride, or ester or amide derived from said high-molecular weight polycarboxylic acid or anhydride, with (C)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal component (C)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(C)(ii) the reaction product of (C)(ii)(a) at least one low-molecular weight polycarboxylic acid or anhydride, or ester or amide derived from said low-molecular weight polycarboxylic acid or anhydride, with (C)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (C)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms;

said components (C)(i) and (C)(ii) being coupled together by (C)(iii) at least one compound having (C)(iii)(a) two or more primary amino groups, (C)(iii)(b) two or more secondary amino groups, (C)(iii)(c) at least one primary amino group and at least one secondary amino group, (C)(iii)(d) at least two hydroxyl groups, or (C)(iii)(e) at least one primary or secondary amino group and at least one hydroxyl group; or

(D) mixture of two or more of (A), (B) and (C);

component (II) comprising:

(A') at least one phosphorus-containing acid represented by the formula ##STR36## wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are independently oxygen or sulfur; a and b are independently zero or one, and R.sup.1 and R.sup.2 are independently hydrocarbyl groups; or

(B') at least one salt derived from said phosphorous-containing acid (A') and at least one metal selected from the group consisting of magnesium, calcium, strontium, chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc, cadmium, aluminum, tin, lead, and mixtures of two or more thereof; or

(C') mixture of (A') and (B');

with the proviso that when component (II) is (A'), component (I) is (B), (C) or a mixture of (B) and (C).

4. A cartridge comprising a cartridge shell containing a cap-sensitive explosive emulsion; said emulsion comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous duel, said carbonaceous fuel comprising at least one wax, and an emulsifying amount of a composition comprising the reaction product of component (I) with component (II);

component (I) comprising:

(A) the reaction product of

(A)(i) at least one carboxylic acid or anhydride, or ester or amide derived from said acid or anhydride, with

(A)(ii) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal; or

(B) a composition comprising

(B)(i) the reaction product of (B)(i)(a) at least one high-molecular weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derived from said high-molecular weight acid or anhydride, with (B)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(B)(ii) the reaction product of (B)(ii)(a) at least one low-molecular weight carboxylic acid or anhydride, or ester or amide derived from said low-molecular weight acid or anhydride, with (B)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms; or

(C) a composition comprising

(C)(i) the reaction product of (C)(i)(a) at least one high-molecular weight hydrocarbyl-substituted polycarboxylic acid or anhydride, or ester or amide derived from s aid high-molecular weight polycarboxylic acid or anhydride, with (C)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (C)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to 500 carbon atoms; and

(C)(ii) the reaction product of (C)(ii)(a) at least one low-molecular weight polycarboxylic acid or anhydride, or ester or amide derived from said low-molecualar weight polycarboxylic acid or anhydride, with (C)(ii)(b) ammonia, at least one amine, at least one alkaIi metal and/or at least one alkaline-earth metal, component (C)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms;

said components (C)(i) and (C)(ii) being coupled together by (C)(iii) at least one compound having (C)(iii)(a) two or more primary amino groups, (C)(iii)(c) at least one primary amino group and at least one secondary amino group, (C)(iii)(d) at least two hydroxyl groups, or (C)(iii)(e) at least one primary or secondary amino group and at least one hydroxyl group; or

(D) mixture of two or more of (A), (B) and (C);

component (II) comprising:

(A') at least one phosphorus-containing acid represented by the formula ##STR37## wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are independently oxygen or sulfur; a and b are independently zero or one, and R.sup.1 and R.sup.2 are independently hydrocarbyl groups; or

(B') at least one salt derived from said phosphorous-containing acid (A') and at least one metal selected from the group consisting of magnesium, calcium, strontium, chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc, cadmium, aluminum, tin, lead, and mixtures or two or more thereof; or

(C') mixture of (A') and (B');

with the proviso that when component (II) is (A'), component (I) is (B), (C) or a mixture of (B) and (C).

5. A cartridge having a diameter of about 1.25 inches or less comprising at least one cap-sensitive explosive emulsion; said emulsion comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, and an emulsifying amount of a composition comprising the reaction product of component (I) with component (II);

component (I) comprising:

(A) the reaction product of

(A)(i) at least one carboxylic acid or anhydride, or ester or amide derived from said acid or anhydride, with

(A)(ii) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal; or

(B) a composition comprising

(B)(i) the reaction product of (B)(i)(a) at least one high-molecular weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derived from said high-molecular weight acid or anhydride, with (B)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(B)(ii) the reaction product of (B)(ii)(a) at least one low-molecular weight carboxylic acid or anhydride, or ester or amide derived form said low-molecular weight acid or anhydride, with (B)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms; or

(C) a composition comprising

(C)(i) the reaction product of (C)(i)(a) at least one high-molecular weight hydrocarbyl-substituted polycarboxylic acid or anhydride, or ester or amide derived from said high-molecular weight polycarboxylic acid or anhydride, with (C)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (C)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(C)(ii) the reaction product of (C)(ii)(a) at least one low-molecular weight polycarboxylic acid or anhydride, or ester or amide derived from said low-molecular weight polycarboxylic acid or anhydride, with (C)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (C)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms;

said components (C)(i) and (C)(ii) being coupled together by (C)(iii) at least one compound having (C)(iii)(a) two or more primary amino groups, (C)(iii)(b) two or more secondary amino groups, (C)(iii)(c) at least one primary group and at least one secondary amino group, (C)(iii)(d) at least two hydroxyl groups, or (C)(iii)(e) at least one primary or secondary amino group and at least one hydroxyl group; or

(D) mixture of two or more of (A), (B) and (C);

component (II) comprising:

(A') at least one phosphorus-containing acid represented by the formula ##STR38## wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are independently oxygen or sulfur; a and b are independently zero or one, and R.sup.1 and R.sup.2 are independently hydrocarbyl groups; or

(B') at least one salt derived from said phosphorous-containing acid (A') and at least one metal selected from the group consisting of magnesium, calcium, strontium, chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc, cadmium, aluminum, tin, lead, and mixtures of two or, more thereof; or

(C') mixture or (A') and (B');

with the proviso that when component (II) is (A'), component (1) is (B), (C) or a mixture of (B) and (C).

TECHNICAL FIELD

This invention relates to novel compositions that have utility as emulsifiers, and to explosive emulsions containing these compositions. More particularly, this invention relates to compositions comprising the reaction product of component (I) with component (II), component (I) comprising certain carboxylic acids or anhydrides, or esters or amides derived therefrom, reacted with ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (II) comprising certain phosphorus-containing acids, or metal salts of said phosphorus-containing acids, the metals being selected from the group consisting of magnesium, calcium, strontium, chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc, cadmium, aluminum, tin, lead, and mixtures of two or more thereof. These compositions are useful as emulsifiers in water-in-oil explosive emulsions.

BACKGROUND OF THE INVENTION

The prior art discloses a large number of dispersants for use in fuels and lubricants which are derivatives of carboxylic acid acylating agents. Typically, the acylating agents are prepared by the reaction of an olefin (e.g., a polyalkylene such as polyisobutylene) or a derivative thereof, containing for example at least about 10 aliphatic carbon atoms and generally at least about 30 or at least about 50 aliphatic carbon atoms, with an unsaturated carboxylic acid or derivative thereof such as acrylic acid, methylacrylate, maleic acid, fumaric acid or maleic anhydride. Dispersants are prepared from the carboxylic acid acylating agents by reaction with, for example, amines characterized by the presence within their structure of at least one N-H group, alcohols, reactive metal or reactive metal compounds, and combinations of the above. The prior art relative to the preparation of such carboxylic acid derivatives is summarized in U.S. Pat. No. 4,234,435.

It also has been suggested that carboxylic acid derivative compositions such as those described above can be post-treated with various reagents to modify and improve the properties of the compositions. Acylated nitrogen compositions prepared by reacting the acylating agents described above with an amine can be post-treated, for example, by contacting the acylated nitrogen compositions thus formed with one or more post-treating reagents such as phosphoric acid, boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acid, carbon disulfide, sulfur, sulfur chlorides, alkenyl cyanides, carboxylic acid acylating agents, aldehydes, ketones, epoxides, etc. Lists of the prior art relating to post-treatment of carboxylic ester and amine dispersants with reagents such as those described above are contained in a variety of patents such as U.S. Pat. No. 4,203,855 (Col. 19, lines 16-24) and U.S. Pat. No. 4,234,435 (Col. 42, lines 33-46).

U.S. Pat. No. 4,234,435 describes lubricating oils containing carboxylic acid derivative compositions prepared by post-treating acylated amines with a variety of post-treating reagents including hydrocarbyl thiophosphates and hydrocarbyl thiophosphites (Col. 41, lines 67-68).

The use of metal salts, expecially zinc salts, of phosphorodithioic acids as extreme pressure (E.P.) agents, corrosion inhibitors and antioxidants in lubricants is disclosed, for example, in U.S. Pat. Nos. 3,390,082; 4,263,150; 4,282,171; 4,289,635; 4,308,154; 4,320,019; 4,357,250; 4,417,990; and 4,446,039.

U.S. Pat. Nos. 4,329,249; 4,368,133; 4,435,297; 4,447,348; 4,448,703; and 4,666,620 disclose the use of nitrogen-containing carboxylic dispersants in water based functional fluids. These dispersants are made by reacting a carboxylic acid acylating agent having at least one hydrocarbyl substituent of from about 12 to about 500 carbon atoms with at least one N-(hydroxyl-substituted hydrocarbyl) amine, hydroxyl-substituted poly(hydrocarbyloxy) analog of said amine, or mixtures thereof. These patents indicate that preferred acylating agents include the substituted succinic acids or anhydrides, such as polyisobutenyl-substituted succinic anhydride, and the amines that are useful include the primary, secondary and tertiary alkanol amines, such as diethylethanolamine. The nitrogen-containing dispersants are useful in dispersing oil-soluble, water-insoluble functional additives in water-based functional fluids. Among the functional additives that can be dispersed is zinc salt of O,O'-di(isooctyl)phosphorodithioic acid.

U.S. Pat. No. 4,772,739 discloses nitrogen- and phosphorus-containing compositions which are useful as E.P., load-carrying and anti-wear agents in water-based functional fluids. The nitrogen- and phosphorus-containing compositions are made by the reaction of (A) at least one carboxylic acid acylating agent, with (B) at least one amine characterized by the presence within its structure of at least one HN<group, and (C) at least one phosphorus-containing acid of the formula ##STR1## wherein each X.sup.1, X.sup.2, X.sup.3 and X.sup.4 is independently oxygen or sulfur, each m is zero or one, and each R.sup.1 and R.sup.2 is independently a hydrocarbyl group.

European Application 0 156 572 discloses compounds which contain a hydrophobic component and a hydrophilic component covalently bonded together which are useful as surfactants in water-in-oil emulsions. The hydrophobic component is a saturated or unsaturated C.sub.30-500 hydrocarbon chain, and the hydrophilic component contains an anionic grouping selected from phosphate, phosphonate, sulphate, sulphonate and carboxymethyl. Example 1 discloses a compound derived from poly(isobutenyl) succinic anhydride, ethanolamine, and phosphoric acid. Other examples indicate that diethanolamine or tris(hydroxymethyl) aminoethane can be substituted for the ethanolamine used in Example 1.

Water-in-oil explosive emulsions typically comprise a discontinuous oxidizer phase comprising at least one oxygen-supplying component such as ammonium nitrate, a continuous organic phase comprising at least one carbonaceous fuel, and an emulsifier Examples of such water-in-oil explosive emulsions are disclosed, inter alia, in U.S. Pat. Nos. 3,447,978; 3,765,964; 3,985,593; 4,008,110; 4,097,316; 4,104,092; 4,110,134; 4,149,916; 4,149,917; 4,218,272; 4,259,977; 4,357,184; 4,371,408; 4,391,659; 4,404,050; 4,409,044; 4,448,619; 4,453,989; and 4,534,809; and U.K. Patent Application 2,050,340A.

U.S. Pat. No. 4,216,040 discloses water-in-oil emulsion blasting agents having a discontinuous aqueous phase, a continuous oil or water-immiscible liquid organic phase, and an organic cationic emulsifier having a lipophilic portion and a hydrophilic portion, the lipophilic portion being an unsaturated hydrocarbon chain.

U.S. Pat. No. 4,708,753 discloses water-in-oil emulsions which comprise (A) a continuous oil phase; (B) a discontinuous aqueous phase; (C) a minor emulsifying amount of at least one salt derived from (C)(I) at least one hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derivative of said acid or anhydride, the hydrocarbyl substituent of (C)(I) having an average of from about 20 to about 500 carbon atoms, and (C)(II) at least one amine; and (D) a functional amount of at least one water-soluble, oil-insoluble functional additive dissolved in said aqueous phase. These emulsions can be explosive emulsions when the functional additive (D) is an oxygen-supplying salt such as ammonium nitrate.

U.S. Pat. No. 4,710,248 discloses an emulsion explosive composition comprising a discontinuous oxidizer-phase dispersed throughout a continuous fuel phase with a modifier comprising a hydrophilic moiety and a lipophilic moiety. The hydrophilic moiety comprises a carboxylic acid or a group capable of hydrolyzing to a carboxylic acid. The lipophilic moiety is a saturated or unsaturated hydrocarbon chain. The emulsion explosive composition pH is above 4.5.

U.S. Pat. No. 4,822,433 discloses an explosive emulsion composition comprising a discontinuous phase containing an oxygen-supplying component and an organic medium forming a continuous phase wherein the oxygen-supplying component and organic medium are capable of forming an emulsion which, in the absence of a supplementary adjuvant, exhibits an electrical conductivity measured at 60.degree. C., not exceeding 60,000 picomhos/meter. The reference indicates that the conductivity may be achieved by the inclusion of a modifier which also functions as an emulsifier. The modifier is comprised of a hydrophilic moiety and a lipophilic moiety. The lipophilic moiety can be derived from a poly[alk(en)yl] succinic anhydride. Poly(isobutylene) succinic anhydride having a number average molecular weight in the range of 400 to 5000 is specifically identified as being useful. The hydrophilic moiety is described as being polar in character, having a molecular weight not exceeding 450 and can be derived from polyols, amines, amides, alkanol amines and heterocyclics. Example 5 of this reference discloses the use as the modifier of a 1:1 condensate of polyisobutenyl succinic anhydride (number average molecular weight=1200) and ethanol amine which had been reacted with one mole of phosphoric acid to form a monophosphate derivative. The emulsifier disclosed in this example is described as being useful in making an emulsion useful for making cartridges.

South African Patent 87/8540 discloses an explosive composition comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one water-immiscible organic liquid, and an emulsifying amount of at least one nitrogen-containing emulsifier derived from (A) at least one carboxylic acylating agent, (B) at least one polyamine, and (C) at least one acid or acid-producing compound capable of forming at least one salt with said polyamine. Examples of (A) include polyisobutenyl succinic acid or anhydride. Examples of (B) include the alkylene polyamines. Examples of (C) include the phosphorus acids (e.g., O,S-dialkylphosphorotrithioic acid). These explosive compositions can be water-in-oil emulsions or melt-in-oil emulsions.

SUMMARY OF THE INVENTION

The present invention provides for a composition comprising the reaction product of component (I) with component (II);

component (I) comprising:

(A) the reaction product of

(A)(i) at least one carboxylic acid or anhydride, or ester or amide derived from said acid or anhydride, with

(A)(ii) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal; or

(B) a composition comprising

(B)(i) the reaction product of (B)(i)(a) at least one high-molecular weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derived from said high-molecular weight acid or anhydride, with (B)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(B)(ii) the reaction product of (B)(ii)(a) at least one low-molecular weight carboxylic acid or anhydride, or ester or amide derived from said low-molecular weight acid or anhydride, with (B)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (B)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms; or

(C) a composition comprising

(C)(i) the reaction product of (C)(i)(a) at least one high-molecular weight hydrocarbyl-substituted polycarboxylic acid or anhydride, or ester or amide derived from said high-molecular weight polycarboxylic acid or anhydride, with (C)(i)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (C)(i)(a) having at least one hydrocarbyl substituent having an average of about 20 to about 500 carbon atoms; and

(C)(ii) the reaction product of (C)(ii)(a) at least One low-molecular weight polycarboxylic acid or anhydride, or ester or amide derived from said low-molecular weight polycarboxylic acid or anhydride, with (C)(ii)(b) ammonia, at least one amine, at least one alkali metal and/or at least one alkaline-earth metal, component (C)(ii)(a) optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms;

said components (C)(i) and (C)(ii) being coupled together by (C)(iii) at least one compound having (C)(iii)(a) two or more primary amino groups, (C)(iii)(b) two or more secondary amino groups, (C)(iii)(c) at least one primary amino group and at least one secondary amino group, (C)(iii)(d) at least two hydroxyl groups, or (C)(iii)(e) at least one primary or secondary amino group and at least one hydroxyl group; or

(D) mixture of two or more of (A), (B) and (C);

component (II) comprising:

(A') at least one phosphorus-containing acid represented by the formula ##STR2## wherein X.sup.1, X.sup.2, X.sup.3 and X.sup.4 are independently oxygen or sulfur; a and b are independently zero or one, and R.sup.1 and R.sup.2 are independently hydrocarbyl groups; or

(B') at least one salt derived from said phosphorous-containing acid (A') and at least one metal selected from the group consisting of magnesium, calcium, strontium, chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc, cadmium, aluminum, tin, lead, and mixtures of two or more thereof; or

(C') mixture of (A') and (B');

with the proviso that when component (II) is (A'), component (I) is (B), (C) or a mixture of (B) and (C). The invention further provides for concentrates comprising the foregoing composition. The invention further provides for explosive emulsions comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, and an emulsifying amount of the foregoing composition.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "emulsion" as used in this specification and in the appended claims is intended to cover not only water-in-oil emulsions, but also explosive compositions derived from such emulsions wherein at temperatures below that at which the emulsion is formed the discontinuous phase is solid or in the form of droplets of super-cooled liquid.

The term "hydrocarbyl" is used herein to include:

(1) hydrocarbyl groups, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl), aromatic, aliphatic- and alicyclic-substituted aromatic groups and the like as well as cyclic groups wherein the ring is completed through another portion of the molecule (that is, any two indicated groups may together form an alicyclic group);

(2) substituted hydrocarbyl groups, that is, those groups containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbyl nature of the hydrocarbyl group; those skilled in the art will be aware of such groups, examples of which include ether, oxo, halo (e.g., chloro and fluoro), alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.;

(3) hetero groups, that is, groups which will, while having predominantly hydrocarbyl character within the context of this invention, contain other than carbon present in a ring or chain otherwise composed of carbon atoms. Suitable heteroatoms will be apparent to those of skill in the art and include, for example, sulfur, oxygen, nitrogen and such substituents as pyridyl, furanyl, thiophenyl, imidazolyl, etc.

In general, no more than about three non-hydrocarbon groups or heteroatoms and preferably no more than one, will be present for each 10 carbon atoms in a hydrocarbyl group. Typically, there will be no such groups or heteroatoms in a hydrocarbyl group and it will, therefore, be purely hydrocarbyl.

The hydrocarbyl groups are preferably free from acetylenic unsaturation; ethylenic unsaturation, when present will generally be such that there is no more than one ethylenic linkage present for every 10 carbon-to-carbon bonds. The hydrocarbyl groups are often completely saturated and therefore contain no ethylenic unsaturation.

The term "lower" as used herein in conjunction with terms such as alkyl, alkenyl, alkoxy, and the like, is intended to describe such groups which contain a total of up to 7 carbon atoms.

The term "water-soluble" refers to materials which are soluble in water to the extent of at least one gram per 100 milliliters of water at 25.degree. C.

The term "oil-soluble" referes to materials which are soluble in mineral oil to the extent of at least one gram per 100 milliliters of oil at 25.degree. C.

Component (A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a) and (C)(ii)(a)

Components (B)(i)(a) and (C)(i)(a) are high-molecular weight hydrocarbyl-substituted carboxylic acids or anhydrides, or esters or amides derived therefrom. Typically these high-molecular weight acids or anhydrides or derivatives have hydrocarbyl substituents containing an average of about 20 to about 500 carbon atoms, more preferably about 30 to about 500 carbon atoms, more preferably about 40 to about 500 carbon atoms, more preferably about 50 to about 500 carbon atoms.

Components (B)(ii)(a) and (C)(ii)(a) are low-molecular weight carboxylic acids or anhydrides, or esters or amides derived therefrom. These low-molecular weight acids or anhydrides or derivatives can optionally include a hydrocarbyl substituent of up to about 18 carbon atoms, preferably about 4 to about 18 carbon atoms, more preferably about 8 to about 18 carbon atoms, more preferably about 10 to about 18 carbon atoms, more preferably about 12 to about 18 carbon atoms, more preferably about 16 to about 18 carbon atoms. The hydrocarbyl substituent can be derived from at least one compound selected from the group consisting of ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1butene, 3-methyl-1-butene, 1-hexene, 1-heptene, 1-octene, styrene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene and 1-octadecene. The hydrocarbyl substituent can be derived from an alpha-olefin fractions such as those selected from the group consisting of C.sub.15-18 alpha-olefins, C.sub.12-16 alpha-olefins, C.sub.14-16 alpha-olefins, C.sub.14-18 alpha-olefins, C.sub.16-18 alpha-olefins, etc.

Component (A)(i) can be either a low-molecular weight or a high-molecular weight carboxylic acid or anhydride, or ester or amide derived therefrom. When the inventive compositions are used as emulsifiers for explosive emulsions, such compositions are soluble in the organic phase of such emulsions. The number of carbon atoms present in component (A)(i) is important in contributing to the desired solubility of these compositions. The sum of the carbon atoms in components (I) and (II) must be sufficient to render the composition oil-soluble. Generally, if component (A)(i) contains a large number of carbon atoms, components (A)(ii) and (II) may be selected from those compounds containing fewer carbon atoms. Conversely, if components (A)(ii) and/or (II) contain a large number of carbon atoms, component (A)(i) can be selected from those compounds containing fewer carbon atoms. Usually, in order to provide the desired hydrocarbon solubility, the sum of the carbon atoms in components (A)(i), (A)(ii) and (II) should total at least about 10 carbon atoms, more preferably at least about 30 carbon atoms, more preferably at least about 50 carbon atoms.

Components (A)(i), (B)(i)(a) and (B)(ii)(a) can be mono- or polycarboxylic acids or anhydrides, or esters or amides derived therefrom. Components (C)(i)(a) and (C)(ii)(a) are polycarboxylic acids or anhydrides, or esters or amides derived therefrom. Each of these components can be aliphatic or aromatic. These components may contain polar substituents provided that the polar substituents are not present in portions sufficiently large to alter significantly the hydrocarbon character of the acylating agent. Typical suitable polar substituents include halo, such as chloro and bromo, oxo, oxy, formyl, sulfenyl, sulfinyl, thio, nitro, etc. Such polar substituents, if present, preferably do not exceed about 10% by weight of the total weight of the hydrocarbon portion of these components, exclusive of the carboxyl groups.

The low-molecular weight monocarboxylic acids contemplated for use in this invention include saturated and unsaturated acids. Examples of such useful acids include formic acid, acetic acid, chloroacetic acid, propionic acid, butyric acid, acrylic, benzoic acid, butanoic acid, cyclohexanoic, dodecanoic acid, palmitic acid, decanoic acid, oleic acid, lauric acid, stearic acid, myristic acid, linoleic acid, linolenic acid, naphthenic acid, chlorostearic acid, tall oil acid, etc. Anhydrides as well as esters and amides derived from these acids can also be used. Mixtures of two or more of the foregoing can also be used.

Examples of low-molecular weight polycarboxylic acids and anhydrides that can be used include dicarboxylic acids and derivatives such as maleic acid, maleic anhydride, chloromaleic anhydride, malonic acid, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, azelaic acid, sebacic acid, glutaconic acid, citraconic acid, itaconic acid, allyl succinic acid, cetyl malonic acid, tetrapropylene-substituted succinic anhydride, etc. Esters and amides derived from these acids and anhydrides can be used.

An extensive discussion of these low-molecular weight carboxylic acids can be found in Kirk-Othmer "Encyclopedia of Chemical Technology" Third Edition, 1978, John Wiley & Sons, New York, pp. 814-871; these pages being incorporated herein by reference.

Low-molecular weight hydrocarbyl-substituted succinic acid and anhydrides can be used. These acids and anhydrides can be represented by the formulae ##STR3## wherein R is a hydrocarbyl group of up to about 18 carbon atoms, preferably about 4 to about 18 carbon atoms, more preferably about 8 to about 18 carbon atoms, more preferably about 10 to about 18 carbon atoms, more preferably about 12 to about 18 carbon atoms, more preferably about 16 to about 18 carbon atoms. Preferably, R is an aliphatic or alicyclic hydrocarbyl group with less than 10% of its carbon-to-carbon bonds being unsaturated. Examples of such groups include 4-butylcyclohexyl, di(isobutyl), decyl, etc. The hydrocarbyl group can be derived from an olefin such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 1-heptene, 1-octene, styrene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, etc. The hydrocarbyl group can also be derived from an olefin fraction such as C.sub.15-18 alpha-olefins, C.sub.12-16 alpha-olefins, C.sub.14-16 alpha-olefins, C.sub.14-18 alpha-olefins, C.sub.16-18 alphaolefins, etc.

The monocarboxylic acids include isoaliphatic acids, i.e., acids having one or more lower acyclic pendant alkyl groups. Such acids often contain a principal chain having from about 14 to about 20 saturated, aliphatic carbon atoms and at least one but usually no more than about four pendant acyclic alkyl groups. These acids are categorized as low-molecular weight or high-molecular weight acids within the scope of the invention depending upon the total number of carbon atoms in the principal chain and pendant groups; low-molecular weight acids have up to about 18 carbon atoms, while high-molecular weight acids have about 20 or more carbon atoms. The principal chain of the acid is exemplified by groups derived from tetradecane, pentadecane, hexadecane, heptadecane, octadecane, and eicosane. The pendant group is preferably a lower alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, or other groups having up to about 7 carbon atoms. The pendant group may also be a polar-substituted alkyl group such as chloromethyl, bromobutyl, methoxyethyl, or the like, but it preferably contains no more than one polar substituent per group. Specific examples of such isoaliphatic acids include 10-methyl-tetradecanoic acid, 11-methyl-pentadecanoic acid, 3-ethyl-hexadecanoic acid, 15-methyl-heptadecanoic acid, 16-methyl-heptadecanoic acid, 6-methyl-octadecanoic acid, 8-methyl-octadecanoic acid, 10-methyl-octadecanoic acid, 14-methyl-octadecanoic acid, 16-methyloctadecanoic acid, 15-ethyl-heptadecanoic acid, 3-chloromethyl-nonadecanoic acid, 7,8,9,10-tetramethyl-octadecanoic acid, and 2,9,10-trimethyl-octadecanoic acid.

The isoaliphatic acids include mixtures of branch-chain acids prepared by the isomerization of commercial fatty acids of, for example, about 16 to about 20 carbon atoms. A useful method involves heating the fatty acid at a temperature above about 250.degree. C. and a pressure between about 200 and 700 psi, distilling the crude isomerized acid, and hydrogenating the distillate to produce a substantially saturated isomerized acid. The isomerization can be promoted by a catalyst such as mineral clay, diatomaceous earth, aluminum chloride, zinc chloride, ferric chloride, or some other Friedel-Crafts catalyst. The concentration of the catalyst may be as low as about 0.01%, but more often from about 0.1% to about 3% by weight of the isomerization mixture. Water also promotes the isomerization and a small amount, from about 0.1% to about 5% by weight, of water may thus be advantageously added to the isomerization mixture. The unsaturated fatty acids from which the isoaliphatic acids may be derived include oleic acid, linoleic acid, linolenic acid, and commercial fatty acid mixtures such as tall oil acids.

The high-molecular weight mono- and polycarboxylic acids and anhydrides are well known in the art and have been described in detail, for example, in the following U.S., British and Canadian patents: U.S. Pat. Nos. 3,024,237; 3,087,936; 3,163,603; 3,172,892; 3,215,707; 3,219,666; 3,231,587; 3,245,910; 3,254,025; 3,271,310; 3,272,743; 3,272,746; 3,278,550; 3,288,714; 3,306,907; 3,307,928; 3,312,619; 3,341,542; 3,346,354; 3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179; 3,454,607; 3,346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169; 3,868,330; 3,912,764; 4,234,435; and 4,368,133; British Pat. Nos. 944,136; 1,085,903; 1,162,436; and 1,440,219; and Canadian Pat. No. 956,397. These patents are incorporated herein by reference for their disclosures of such acids and anhydrides and the methods for making them.

As disclosed in the foregoing patents, there are several processes for preparing these high-molecular weight acids and anhydrides. Generally, these processes involve the reaction of (1) an ethylenically unsaturated carboxylic acid, acid halide, anhydride or ester reactant with (2) an ethylenically unsaturated hydrocarbon or a chlorinated hydrocarbon at a temperature within the range of about 100.degree.-300.degree. C. The chlorinated hydrocarbon or ethylenically unsaturated hydrocarbon reactant preferably contains at least about 10 carbon atoms, more preferably at least about 20 carbon atoms, more preferably at least about 30 carbon atoms, more preferably at least about 40 carbon atoms, more preferably at least about 50 carbon atoms, and may contain polar substituents, oil-solubilizing pendant groups, and be unsaturated within the general limitations explained hereinabove.

When preparing the hydrocarbyl-substituted carboxylic acids, the carboxylic acid reactant usually corresponds to the formula R.sub.o -(COOH).sub.n, where R.sub.o is characterized by the presence of at least one ethylenically unsaturated carbon-to-carbon covalent bond and n is an integer from 1 to about 6 and preferably 1 or 2. The acidic reactant can also be the corresponding carboxylic acid halide, anhydride, ester, or other equivalent acylating agent and mixtures of one or more of these. Ordinarily, the total number of carbon atoms in the acidic reactant will not exceed about 20, preferably this number will not exceed about 10 and generally will not exceed about 6. Preferably the acidic reactant will have at least one ethylenic linkage in an alpha-, beta-position with respect to at least one carboxyl function. Exemplary acidic reactants are acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, glutaconic acid, chloromaleic acid, aconitic acid, crotonic acid, methylcrotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid, and the like. Preferred acid reactants include acrylic acid, methacrylic acid, maleic acid, and maleic anhydride.

The ethylenically unsaturated hydrocarbon reactant and the chlorinated hydrocarbon reactant used in the preparation of these high-molecular weight carboxylic acids and anhydrides can be high molecular weight, substantially saturated petroleum fractions and substantially saturated olefin polymers and the corresponding chlorinated products. Polymers and chlorinated polymers derived from mono-olefins having from 2 to about 30 carbon atoms, preferably 2 to about 20 carbon atoms, more preferably 2 to about 12 carbon atoms, more preferably 2 to about 8 carbon atoms, more preferably 2 to about 6 carbon atoms are useful. Useful polymers are the polymers of 1-mono-olefins such as ethylene, propene, 1-butene, isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene, 3-cyclohexyl-1-butene, and 2-methyl-5-propyl-1-hexene. Polymers of medial olefins, i.e., olefins in which the olefinic linkage is not at the terminal position, likewise are useful. These are exemplified by 2-butene, 3-pentene, 4-octene, etc.

Interpolymers of 1-mono-olefins such as illustrated above with each other and with other interpolymerizable olefinic substances such as aromatic olefins, cyclic olefins, and polyolefins, are also useful sources of the ethylenically unsaturated reactant. Such interpolymers include for example, those prepared by polymerizing isobutene with styrene, isobutene with butadiene, propene with isoprene, propene with isobutene, ethylene with piperylene, isobutene with chloroprene, isobutene with p-methyl-styrene, 1-hexene with 1,3-hexadiene, 1-octene with 1-hexene, 1-heptene with 1-pentene, 3-methyl-1-butene with 1-octene, 3,3-dimethyl-1-pentene with 1-hexene, isobutene with styrene and piperylene, etc.

For reasons of hydrocarbon solubility, the interpolymers contemplated for use in preparing the high-molecular weight carboxylic acids and anhydrides of this invention are preferably substantially aliphatic and substantially saturated. That is, they should contain at least about 80% and preferably at least about 95%, on a weight basis, of units derived from aliphatic mono- olefins. Preferably, they contain no more than about 5% olefinic linkages based on the total number of the carbon-to-carbon covalent linkages present.

In one embodiment of the invention, the polymers and chlorinated polymers are obtained by the polymerization of a C.sub.4 refinery stream having a butene content of about 35% to about 75% by weight and an isobutene content of about 30% to about 60% by weight in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride. These polyisobutenes preferably contain predominantly (that is, greater than about 80% of the total repeat units) isobutene repeat units of the configuration. ##STR4##

The chlorinated hydrocarbons and ethylenically unsaturated hydrocarbons used in the preparation of the high-molecular weight carboxylic acids and anhydrides preferably have up to about 500 carbon atoms per molecule. Preferred high-molecular weight carboxylic acids and anhydrides are those containing hydrocarbyl groups of from about 20 to about 500 carbon atoms, more preferably from about 30 to about 500 carbon atoms, more preferably from about 40 to about 500 carbon atoms, more preferably from about 50 to about 500 carbon atoms.

The high-molecular weight carboxylic acids and anhydrides may also be prepared by halogenating a high molecular weight hydrocarbon such as the above-described olefin polymers to produce a polyhalogenated product, converting the polyhalogenated product to a polynitrile, and then hydrolyzing the polynitrile. They may be prepared by oxidation of a high molecular weight polyhydric alcohol with potassium permanganate, nitric acid, or a similar oxidizing agent. Another method involves the reaction of an olefin or a polar-substituted hydrocarbon such as a chloropolyisobutene with an unsaturated polycarboxylic acid such as 2-pentene-1,3,5-tricarboxylic acid prepared by dehydration of citric acid.

The high-molecular weight carboxylic acid and anhydrides can also be obtained by reacting chlorinated carboxylic acids, anhydrides, acyl halides, and the like with ethylenically unsaturated hydrocarbons or ethylenically unsaturated substituted hydrocarbons such as the polyolefins and substituted polyolefins described hereinbefore in the manner described in U.S. Pat. No. 3,340,281, this patent being incorporated herein by reference.

The low- and high-molecular weight carboxylic acid anhydrides can be obtained by dehydrating the corresponding acids. Dehydration is readily accomplished by heating the acid to a temperature above about 70.degree. C., preferably in the presence of a dehydration agent, e.g., acetic anhydride. Cyclic anhydrides are usually obtained from polycarboxylic acids having acid groups separated by no more than three carbon atoms such as substituted succinic or glutaric acid, whereas linear anhydrides are usually obtained from polycarboxylic acids having the acid groups separated by four or more carbon atoms.

The low-molecular weight and high-molecular weight carboxylic acids used herein include acid-producing derivatives thereof (in addition to the anhydrides) such as acyl halides and the like. Thus, the term "carboxylic acid" when used in the claims herein also refers to the acyl halides of such acids. These acyl halides can be prepared by the reaction of the carboxylic acids or their anhydrides with a halogenating agent such as phosphorus tribromide, phosphorus pentachloride or thionyl chloride using known techniques.

Hydrocarbyl-substituted succinic acids and anhydrides are preferred high-molecular weight carboxylic acids and anhydrides. These acids and anhydrides can be prepared by reacting maleic anhydride with an olefin or a chlorinated hydrocarbon such as a chlorinated polyolefin. The reaction involves merely heating the two reactants at a temperature in the range of about 100.degree. C. to about 300.degree. C., preferably, about 100.degree. C. to about 200.degree. C. The product from this reaction is a hydrocarbyl-substituted succinic anhydride wherein the substituent is derived from the olefin or chlorinated hydrocarbon. The product may be hydrogenated to remove all or a portion of any ethylenically unsaturated covalent linkages by standard hydrogenation procedures, if desired. The hydrocarbyl-substituted succinic anhydrides may be hydrolyzed by treatment with water or steam to the corresponding acid. The high-molecular weight hydrocarbyl-substituted succinic acids and anhydrides can be represented by the formulae ##STR5## wherein R is the hydrocarbyl substituent. Preferably R contains from about 20 to about 500 carbon atoms, more preferably from about 30 to about 500 carbon atoms, more preferably from about 40 to about 500 carbon atoms, more preferably from about 50 to about 500 carbon atoms.

The Alcohols Useful In Making the Carboxylic Acid Ester Derivatives (A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a) and (C)(ii)(a)

The alcohols useful in making the carboxylic acid ester derivatives (A)(i), (B)(i)(a), (B)(ii)(a), (C)(i)(a) and (C)(ii)(a) of this invention include those compounds of the general formula:

R.sub.1 --(OH).sub.m

wherein R.sub.1 is a monovalent or polyvalent organic group joined to the --OH groups through carbon-to-oxygen bonds (that is, --COH wherein the carbon is not part of a carbonyl group) and m is an integer of from 1 to about 10, preferably 2 to about 6. These alcohols can be aliphatic, cycloaliphatic, aromatic, and heterocyclic, including aliphatic-substituted cycloaliphatic alcohols, aliphatic-substituted aromatic alcohols, aliphatic-substituted heterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols, cycloaliphatic-substituted heterocyclic alcohols, heterocyclic-substituted aliphatic alcohols, heterocyclic-substituted cycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols. Except for the polyoxyalkylene alcohols, the mono- and polyhydric alcohols corresponding to the formula R.sub.1 (OH).sub.m preferably contain not more than about 40 carbon atoms, more preferably not more than about 20 carbon atoms. The alcohols may contain non-hydrocarbon substituents or groups which do not interfere with the reaction of the alcohols with the hydrocarbyl-substituted carboxylic acids or anhydrides of this invention. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl, mercapto, nitro, and interrupting groups such as --O-- and --S-- (e.g., as in such groups as --CH.sub.2 CH.sub.2 --X--CH.sub.2 CH.sub.2 -- where X is --O-- or --S--).

Among the polyoxyalkylene alcohols suitable for use in the preparation of the ester derivatives of this invention are the commercially available polyoxyalkylene alcohols that include the polyoxyethylated amines, amides, and quaternary salts available from Armour Industrial Chemical Co. under the names ETHODUOMEEN polyethoxylated high-molecular-weight aliphatic diamines; ETHOMEEN, polyethoxylated aliphatic amines containing alkyl groups in the range of about 8 to about 18 carbon atoms; ETHOMID, polyethoxylated high-molecular-weight amides; and ETHOQUAD, polyethoxylated quaternary ammonium chlorides derived from long-chain amines.

Useful polyoxyalkylene alcohols and derivatives thereof include the hydrocarbyl ethers and the carboxylic acid esters obtained by reacting the alcohols with various carboxylic acids. Illustrative hydrocarbyl groups are alkyl, cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyl, etc., containing up to about 40 carbon atoms. Specific hydrocarbyl groups include methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl, p-octylphenyl ethyl, cyclohexyl, and the like. Carboxylic acids useful in preparing the ester derivatives are mono- or polycarboxylic acids such as acetic acid, valeric acid, lauric acid, stearic acid, succinic acid, and alkyl or alkenyl-substituted succinic acids wherein the alkyl or alkenyl group contains up to about 20 carbon atoms. Members of this class of alcohols are commercially available from various sources; e.g., PLURONICS, polyols available from Wyandotte Chemicals Corporation; POLYGLYCOL 112-2, a liquid triol derived from ethyleneoxide and propylene-oxide available from Dow Chemical Co.; and TERGITOLS, dodecylphenyl or nonylphenyl polyethylene glycol ethers, and UCONS, polyalkylene glycols and various derivatives thereof, both available from Union Carbide Corporation. However, the alcohols used must have an average of at least one free alcoholic hydroxyl group per molecule of polyoxyalkylene alcohol. For purposes of describing these polyoxyalkylene alcohols, an alcoholic hydroxyl group is one attached to a carbon atom that does not form part of an aromatic nucleus.

Alcohols useful in this invention also include alkylene glycols and polyoxyalkylene alcohols such as polyoxyethylene alcohols, polyoxypropylene alcohols, polyoxybutylene alcohols, and the like. These polyoxyalkylene alcohols (sometimes called polyglycols) can contain up to about 150 oxyalkylene groups, with the alkylene group containing from about 2 to about 8 carbon atoms. Such polyoxyalkylene alcohols are generally dihydric alcohols. That is, each end of the molecule terminates with an OH group. In order for such polyoxyalkylene alcohols to be useful, there must be at least one such OH group. However, the remaining OH group can be esterified with a monobasic, aliphatic or aromatic carboxylic acid of up to about 20 carbon atoms such as acetic acid, propionic acid, oleic acid, stearic acid, benzoic acid, and the like. The monoethers of these alkylene glycols and polyoxyalkylene glycols are also useful. These include the monoaryl ethers, monoalkyl ethers, and monoaralkyl ethers of these alkylene glycols and polyoxyalkylene glycols. This group of alcohols can be represented by the formula

HO--(--R.sub.A O--).sub.p R.sub.B --OR.sub.C

wherein R.sub.A and R.sub.B are independently alkylene groups of from about 2 to 8 carbon atoms; and R.sub.C is aryl (e.g., phenyl), lower alkoxy phenyl, or lower alkyl phenyl, or lower alkyl (e.g., ethyl, propyl, terbutyl, pentyl, etc.); and aralkyl (e.g., benzyl, phenylethyl, phenylpropyl, p-ethylphenylethyl, etc.); p is from zero to about eight, preferably from about 2 to 4. Polyoxyalkylene glycols where the alkylene groups are ethylene or propylene and p is at least two as well as the monoethers thereof as described above are useful.

The monohydric and polyhydric alcohols useful in this invention include monohydroxy and polyhydroxy aromatic compounds. Monohydric and polyhydric phenols and naphthols are preferred hydroxyaromatic compounds. These hydroxy-substituted aromatic compounds may contain other substituents in addition to the hydroxy substituents such as halo, alkyl, alkenyl, alkoxy, alkylmercapto, nitro and the like. Usually, the hydroxy aromatic compound will contain from 1 to about 4 hydroxy groups. The aromatic hydroxy compounds are illustrated by the following specific examples: phenol, p-chlorophenol, p-nitrophenol, beta-naphthol, alpha-naphthol, cresols, resorcinol, catechol, carvacrol, thymol, eugenol, p,p'-dihydroxy-biphenyl, hydroquinone, pyrogallol, phloroglucinol, hexylresorcinol, orcin, quaiacol, 2-chlorophenol, 2,4-dibutylphenol, propene-tetramer-substituted phenol, didodecylphenol, 4,4'-methylene-bis-methylene-bis-phenol, alpha-decyl-beta-naphthol, polyisobutenyl-(molecular weight of about 1000)-substituted phenol, the condensation product of heptylphenol with about 0.5 mole of formaldehyde, the condensation product of octylphenol with acetone, di(hydroxyphenyl)oxide, di-(hydroxyphenyl)sulfide, di(hydroxyphenyl)-disulfide, and 4-cyclohexylphenol.